KR102494931B1 - Non-halogen flame-retardant polyamide/polyester alloy resin composition with improved flame retardancy and molded article comprising the same - Google Patents

Abstract

The present invention relates to a polyamide/polyester alloy resin composition with improved flame retardancy and a molded product including the same, and more specifically, to a polyamide/polyester alloy-based resin composition containing a non-halogen flame retardant, an inorganic filler and a polysiloxane- The present invention relates to a polyamide/polyester alloy resin composition capable of exhibiting improved fluidity and realizing high flame retardancy and dimensional stability in various usage environments and thicknesses by including a polycarbonate copolymer in a specific amount, and a molded product including the same.

Description

Non-halogen flame retardant polyamide/polyester alloy resin composition with improved flame retardancy and molded article including the same

The present invention relates to a polyamide/polyester alloy resin composition with improved flame retardancy and a molded product including the same, and more specifically, to a polyamide/polyester alloy-based resin composition containing a non-halogen flame retardant, an inorganic filler and a polysiloxane- The present invention relates to a polyamide/polyester alloy resin composition capable of exhibiting improved fluidity and realizing high flame retardancy and dimensional stability in various usage environments and specimen thicknesses by including a polycarbonate copolymer in a specific content, and a molded article including the same.

Polyamide resins are basically excellent in mechanical properties, electrical properties, chemical resistance, etc., and are used in various fields such as electrical and electronic, machinery, and automobile industry parts. These parts are electrical connectors and parts related to charging, and they require basic flame retardant performance in various environments, and as technology develops, more detailed and sophisticated parts are required.

However, in the case of polyamide resin, there is a fatal disadvantage in that dimensional change and physical property reduction are caused by moisture. This may act as a defect in a use environment where repetitive external force is applied or precise design is required, and it leads to damage to the fastening part. In addition, when a large amount of flame retardant is used to exhibit high flame retardant performance, the flame retardant contained in the resin composition causes deterioration of mechanical and electrical properties, resulting in a conflict between flame retardant performance and mechanical properties, and excessive cost increase. Occurs.

In order to compensate for the disadvantages of polyamide resins, a method of improving dimensional stability by alloying polyester resins, especially polyethylene terephthalate resins with excellent electrical/physical properties, with polyamide resins has been studied, but deterioration in exterior surface characteristics or mechanical Deterioration of physical properties has been pointed out as a problem.

For example, Korean Patent Publication No. 10-2013-0061388 discloses a resin composition including an alloy resin of polyamide and polyethylene terephthalate, glass fibers, etc., but this is not aimed at improving flame retardancy, and the exterior surface There was a problem of deterioration of properties or mechanical properties.

Therefore, it is necessary to research a technology for realizing high flame retardancy, excellent mechanical properties, and particularly high dimensional stability in various use environments and uses as an electrical connector part.

An object of the present invention is to include a non-halogen flame retardant, an inorganic filler, and a polysiloxane-polycarbonate copolymer in a specific amount in a polyamide/polyester alloy-based resin composition, thereby improving the non-halogen flame retardant polyamide resin composition. It is to provide a polyamide/polyester alloy resin composition capable of exhibiting fluidity and implementing high flame retardancy and dimensional stability in various usage environments and thicknesses, and a molded product including the same.

In order to solve the above technical problem, the present invention, based on 100 parts by weight of the total composition, (1) 25 to 50 parts by weight of a polyamide resin; (2) 5 to 32 parts by weight of a polyester resin; (3) 2 to 13 parts by weight of a polysiloxane-polycarbonate copolymer resin; (4) 5 to 20 parts by weight of a phosphorus-based flame retardant; (5) 15 to 40 parts by weight of an inorganic filler; it provides a polyamide / polyester alloy resin composition containing.

According to another aspect of the present invention, a molded article comprising the polyamide/polyester alloy resin composition of the present invention is provided.

Since the polyamide/polyester alloy resin composition of the present invention realizes excellent flame retardancy at various thicknesses and at the same time exhibits excellent flowability and dimensional stability, it requires sophisticated molding and requires high flame retardant performance and stable dimensions. It can be suitably used in the manufacture of parts and connectors.

Hereinafter, the present invention will be described in more detail.

The polyamide/polyester alloy resin composition of the present invention, based on 100 parts by weight of the total composition, (1) 25 to 50 parts by weight of a polyamide resin; (2) 5 to 32 parts by weight of a polyester resin; (3) 2 to 13 parts by weight of a polysiloxane-polycarbonate copolymer resin; (4) 5 to 20 parts by weight of a phosphorus-based flame retardant; (5) 15 to 40 parts by weight of an inorganic filler;

(1) Polyamide resin

The polyamide resin that can be used in the present invention is not particularly limited as long as it is generally used in the art. In one embodiment, the relative viscosity of the polyamide resin may range from 2.3 to 3.0, more specifically from 2.5 to 2.9, and even more specifically from 2.6 to 2.8. If the relative viscosity of the polyamide resin is less than 2.3, tensile strength, impact strength, and heat resistance are lowered, and if the relative viscosity exceeds 3.0, fluidity during molding may be insufficient, resulting in poor injection molding processability.

In one embodiment, the content of the polyamide resin in the polyamide resin composition of the present invention may be 25 parts by weight or more, 28 parts by weight or more, 30 parts by weight or more, or 35 parts by weight or more based on 100 parts by weight of the total composition. It may be 48 parts by weight or less, 46 parts by weight or less, or 44 parts by weight or less, for example, 25 to 50 parts by weight, 30 to 50 parts by weight, 30 to 45 parts by weight, or 35 to 44 parts by weight. . If the polyamide resin content in 100 parts by weight of the polyamide resin composition of the present invention is less than the above range, there may be problems in that impact strength, tensile strength, and flexural strength are lowered, appearance surface characteristics are lowered, and extrusion processability is also lowered. If it exceeds, there may be a problem in that the water absorption rate increases and the dimensional stability is lowered and the flame retardant effect is relatively lowered.

(2) polyester resin

As the polyester resin used in the present invention, an aromatic polyester resin may be used, and for example, a resin obtained by melt polymerization from terephthalic acid or a terephthalic acid alkyl ester and a glycol component having 2 to 10 carbon atoms may be used. there is. In this case, the alkyl means an alkyl having 1 to 10 carbon atoms.

Specific examples of the aromatic polyester resin include polyethylene terephthalate resin, polytrimethylene terephthalate resin, polybutylene terephthalate resin, polyhexamethylene terephthalate resin, polycyclohexane dimethylene terephthalate resin, any one of these resins. A polyester resin modified to be amorphous by mixing some other monomers or a mixture thereof may be used, and examples thereof include polyethylene terephthalate resin, polytrimethylene terephthalate resin, and polybutylene. A terephthalate resin, an amorphous polyethylene terephthalate resin, etc. can be used.

The polyester resin preferably has an intrinsic viscosity [IV] of 0.6 to 1.5 dl/g, more preferably from 0.7 to 0.9 dl/g. When the polyester resin has an intrinsic viscosity [η] within the above range, excellent mechanical properties and moldability can be secured.

Among the polyester resins, according to one embodiment of the present invention, polyethylene terephthalate may be used.

(2) The content of the polyester resin of the present invention may be 5 parts by weight or more, 8 parts by weight or more, or 10 parts by weight or more, based on 100 parts by weight of the total composition, and 32 parts by weight or less, 30 parts by weight or less, 25 parts by weight or less. Or it may be 20 parts by weight or less, for example, 5 to 32 parts by weight, 5 to 30 parts by weight, 8 to 25 parts by weight, or 10 to 20 parts by weight. If the polyester resin is less than the above range, there may be a problem that the water absorption rate is increased and the dimensional stability is lowered, the flame retardancy is relatively low, and the extrusion processability may also be lowered. If the above range is exceeded, the solidification rate may be slowed, resulting in a decrease in productivity and a decrease in appearance surface characteristics and mechanical strength.

(3) polysiloxane-polycarbonate copolymer resin

The polyamide/polyester alloy resin composition of the present invention may include a polysiloxane-polycarbonate copolymer resin, and the polysiloxane-polycarbonate copolymer resin may include a hydroxy-terminated siloxane and a polycarbonate block as repeating units. there is.

In the present invention, the weight average molecular weight (Mw) of the hydroxy-terminated siloxane included in the polysiloxane-polycarbonate copolymer resin is 2,500 to 15,000, preferably 3,500 to 13,000, more preferably 4,000 to 9,000. If the weight average molecular weight of the hydroxy-terminated siloxane is less than 2,500, the effect of improving impact strength may be insignificant, and if it exceeds 15,000, the reactivity is poor, which may cause problems in synthesizing the polysiloxane-polycarbonate copolymer at a desired molecular weight.

The preferred content of the hydroxy-terminated siloxane in the polysiloxane-polycarbonate copolymer resin of the present invention is 1 to 10% by weight, more preferably 5 to 9% by weight based on 100% by weight of the copolymer. If the content of hydroxy-terminated siloxane is less than 5% by weight, the degree of improvement in flame retardant performance may be insignificant, and if the content exceeds 10% by weight, physical properties such as compatibility and heat resistance may be deteriorated, and manufacturing cost increases, resulting in an economical undesirable from the point of view

According to one preferred embodiment of the present invention, the hydroxy-terminated siloxane in the polysiloxane-polycarbonate copolymer resin has the following formula (1) or formula (1a):

[Formula 1]

In Formula 1,

R ₁ independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 13 carbon atoms, or an aryl group having 6 to 10 carbon atoms. For example, the halogen atom may be Cl or Br, the alkyl group may be an alkyl group having 1 to 13 carbon atoms, such as methyl, ethyl, or propyl, and the alkoxy group may be an alkoxy group having 1 to 13 carbon atoms, such as methoxy, It may be ethoxy or propoxy, and the aryl group may be 6 to 10 aryl groups, such as phenyl, chlorophenyl or tolyl.

R ₂ independently represents a hydrocarbon group having 1 to 13 carbon atoms or a hydroxy group. For example, R ₂ is an alkyl group or alkoxy group having 1 to 13 carbon atoms, an alkenyl group or alkenyloxy group having 2 to 13 carbon atoms, a cycloalkyl group or cycloalkoxy group having 3 to 6 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, It may be an aralkyl group or aralkoxy group having 7 to 13 carbon atoms, or an alkaryl group or alkaryloxy group having 7 to 13 carbon atoms.

R ₃ independently represents an alkylene group having 2 to 8 carbon atoms.

m is independently an integer of 0 to 4;

n is an integer of 30 to 200, preferably an integer of 40 to 170, more preferably an integer of 50 to 120.

)를 사용할 수 있으나, 반드시 이에 한정되는 것은 아니다.In one embodiment, the hydroxy-terminated siloxane of Formula 1 is Dow Corning's siloxane monomer (

) can be used, but is not necessarily limited thereto.

[Formula 1a]

In Formula 1a,

R ₁ , R ₂ , R ₃ and m are as defined in Formula 1 above, and n is independently an integer of 15 to 100, preferably an integer of 20 to 80, and more preferably an integer of 25 to 60. and A represents a structure of Formula 2 or 3 below.

[Formula 2]

In Formula 2, X is Y or NH-Y-NH, where Y is a linear or branched aliphatic group having 1 to 20 carbon atoms, a cycloalkylene group (eg, a cycloalkylene group having 3 to 6 carbon atoms), or a halogen. represents a mononuclear or polynuclear arylene group having 6 to 30 carbon atoms, substituted or unsubstituted with atoms, alkyl groups, alkoxy groups, aryl groups or carboxyl groups. For example, Y is an aliphatic group that is unsubstituted or substituted with a halogen atom, an aliphatic group containing oxygen, nitrogen or sulfur atoms in the main chain, or an aryl that can be derived from bisphenol A, resorcinol, hydroquinone or diphenylphenol. It may be a rene group, and may be represented, for example, by the following Chemical Formulas 2a to 2h.

[Formula 2a]

[Formula 2b]

[Formula 2c]

[Formula 2d]

[Formula 2e]

[Formula 2f]

[Formula 2g]

[Formula 2h]

[Formula 3]

In Formula 3, R ₄ represents an aromatic hydrocarbon group having 6 to 30 carbon atoms, a mixed aromatic/aliphatic hydrocarbon group, or an aliphatic hydrocarbon group having 1 to 20 carbon atoms. Here, R ₄ may have a structure including a halogen, oxygen, nitrogen or sulfur in addition to a carbon atom. For example, R ₄ can be phenyl, chlorophenyl or tolyl (preferably phenyl).

In one embodiment, the hydroxy-terminated siloxane of Chemical Formula 1a may be a reaction product of the hydroxy-terminated siloxane of Chemical Formula 1 (provided that n is an integer from 15 to 100) and an acyl compound. Here, the acyl compound may have, for example, an aromatic, aliphatic, or mixed structure including both aromatic and aliphatic. When the acyl compound is aromatic or mixed, it may have 6 to 30 carbon atoms, and when it is aliphatic, it may have 1 to 20 carbon atoms. The acyl compound may further include a halogen, oxygen, nitrogen or sulfur atom.

In another embodiment, the hydroxy-terminated siloxane of Formula 1a may be a reaction product of a hydroxy-terminated siloxane of Formula 1 (where n is an integer from 15 to 100) and a diisocyanate compound. Here, the diisocyanate compound may be, for example, 1,4-phenylene diisocyanate, 1,3-phenylene diisocyanate or 4,4'-methylenediphenyl diisocyanate.

In another embodiment, the hydroxy-terminated siloxane of Formula 1a is a reaction product of a hydroxy-terminated siloxane of Formula 1 (where n is an integer from 15 to 100) and a phosphorus-containing compound (aromatic or aliphatic phosphate compound) can Here, the phosphorus-containing compound may be represented by Formula 1b below.

[Formula 1b]

In Formula 1b, R ₄ is as defined in Formula 3 above, and Z independently represents phosphorus, a halogen atom, a hydroxyl group, a carboxyl group, an alkyl group (having 1 to 20 carbon atoms), an alkoxy group, or an aryl group.

In addition, according to one preferred embodiment of the present invention, the polycarbonate block in the polysiloxane-polycarbonate copolymer has the following formula (4):

[Formula 4]

In Chemical Formula 4, R ₅ is a divalent (divalent) alkyl group having 1 to 20 carbon atoms (eg, a divalent alkyl group having 1 to 13 carbon atoms), a cycloalkyl group (eg, a divalent cycloalkyl group having 3 to 6 carbon atoms) , an alkenyl group (eg, a divalent alkenyl group having 2 to 13 carbon atoms), an alkoxy group (eg, a divalent alkoxy group having 1 to 13 carbon atoms), or a halogen atom or nitro substituted or unsubstituted or having 6 to 30 carbon atoms Represents a divalent aromatic hydrocarbon group.

Here, the aromatic hydrocarbon group may be derived from a compound having a structure of Formula 4a below.

[Formula 4a]

In Formula 4a, X is an alkylene group, a linear, branched or cyclic alkylene group having no functional group, or a linear, branched or cyclic alkylene group containing a functional group such as sulfide, ether, sulfoxide, sulfone, ketone, naphthyl, or isobutylphenyl. represents a branched or cyclic alkylene group, preferably, X may be a straight, branched or C3-C6 cyclic alkylene group having 1 to 10 carbon atoms; R ₆ independently represents a hydrogen atom, a halogen atom, or an alkyl group such as a straight, branched or cyclic alkyl group having 1 to 20 carbon atoms or 3 to 20 carbon atoms (preferably 3 to 6 carbon atoms); n and m are independently integers from 0 to 4.

The compound of Formula 4a is, for example, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)naphthylmethane, bis(4-hydroxyphenyl) )-(4-isobutylphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1-ethyl-1,1-bis(4-hydroxyphenyl)propane, 1-phenyl-1,1 -Bis(4-hydroxyphenyl)ethane, 1-naphthyl-1,1-bis(4-hydroxyphenyl)ethane, 1,2-bis(4-hydroxyphenyl)ethane, 1,10-bis( 4-hydroxyphenyl) decane, 2-methyl-1,1-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy Phenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) hexane, 2,2-bis (4-hydroxyphenyl) nonane, 2,2- Bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3-fluoro-4-hydroxyphenyl)propane, 4-methyl-2,2-bis(4-hydroxyphenyl)pentane , 4,4-bis (4-hydroxyphenyl) heptane, diphenyl-bis (4-hydroxyphenyl) methane, resorcinol, hydroquinone, 4,4'-dihydroxyphenyl ether [bis(4-hydroxyphenyl) ether], 4,4'-dihydroxy-2,5-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether , bis(3,5-dimethyl-4-hydroxyphenyl) ether, bis(3,5-dichloro-4-hydroxyphenyl) ether, 1,4-dihydroxy-2,5-dichlorobenzene, 1, 4-dihydroxy-3-methylbenzene, 4,4'-dihydroxydiphenol [p,p'-dihydroxyphenyl], 3,3'-dichloro-4,4'-dihydroxyphenyl, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)cyclohexane, 1,1-bis(3,5-dichloro-4- Hydroxyphenyl) cyclohexane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclododecane, 1,1-bis (4-hydroxyphenyl) cyclododecane, 1,1-bis (4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)decane, 1,4-bis(4-hydroxyphenyl)propane, 1,4-bis(4-hydroxyphenyl)butane , 1,4-bis (4-hydroxyphenyl)isobutane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(3-chloro-4-hydroxyphenyl)propane, bis(3,5-dimethyl- 4-hydroxyphenyl)methane, bis(3,5-dichloro-4-hydroxyphenyl)methane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis( 3,5-dibromo-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,4-bis(4-hydroxyphenyl)-2 -methyl-butane, 4,4'-thiodiphenol [bis(4-hydroxyphenyl)sulfone], bis(3,5-dimethyl-4-hydroxyphenyl)sulfone, bis(3-chloro-4-hydroxy hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfoxide, bis(3-methyl-4-hydroxyphenyl)sulfide, bis(3,5-dimethyl-4- Hydroxyphenyl) sulfide, bis(3,5-dibromo-4-hydroxyphenyl) sulfoxide, 4,4'-dihydroxybenzophenone, 3,3',5,5'-tetramethyl-4 ,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenyl, methylhydroquinone, 1,5-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene, but is not limited thereto. . Representative of these is 2,2-bis(4-hydroxyphenyl)propane (bisphenol A). Other functional dihydric phenols may be referred to US Patents US 2,999,835, US 3,028,365, US 3,153,008 and US 3,334,154, and the dihydric phenols may be used alone or in combination of two or more. can be used

In the case of the carbonate precursor, as other monomers of the polycarbonate resin, for example, carbonyl chloride (phosgene), carbonyl bromide, bis halo formate, diphenyl carbonate or dimethyl carbonate can be used.

The preferred viscosity average molecular weight (Mv) of the polysiloxane-polycarbonate copolymer used in the present invention is 15,000 to 30,000, more preferably 17,000 to 22,000. If the viscosity average molecular weight of the polysiloxane-polycarbonate copolymer is less than 15,000, mechanical properties may be significantly lowered, and if it exceeds 30,000, problems may arise in processing the resin due to an increase in melt viscosity.

The content of the polysiloxane-polycarbonate copolymer resin included in the polyamide/polyester alloy resin composition of the present invention may be 2 parts by weight or more, 2.5 parts by weight or more, or 3 parts by weight or more based on 100 parts by weight of the total composition, 13 parts by weight or less, 12 parts by weight or less, 11 parts by weight or less, 10 parts by weight or less, 9 parts by weight or less, 8 parts by weight or less, 7 parts by weight or less, or 6 parts by weight or less, for example 2 to 13 parts by weight , 2 to 12 parts by weight, 2 to 10 parts by weight, 2 to 8 parts by weight, 2 to 6 parts by weight, or 3 to 6 parts by weight. When the content of the polysiloxane-polycarbonate copolymer resin is less than the above range, there may be a problem in that impact strength and fluidity are lowered, and when it exceeds the above range, there may be a problem in that compatibility is lowered and extrusion molding processability is lowered.

(4) Phosphorus flame retardant

The present invention may include a non-halogen flame retardant without any particular limitation, but preferably includes a phosphorus-based flame retardant. In the case of halogen-based flame retardants, substances harmful to the human body are generated, but phosphorus-based flame retardants of the present invention, particularly phosphinate-based flame retardants, do not generate halogen-based gases during processing, molding or combustion, so they are environmentally friendly.

In the polyamide/polyester alloy resin composition of the present invention, the phosphorus-based flame retardant means a conventional flame retardant containing phosphorus, for example, phosphate, phosphonate, phosphinate, Phosphine oxide, phosphazene, and metal salts thereof may be used, but are not limited thereto.

For example, the phosphorus-based flame retardant may be represented by Formula 5 below.

[Formula 5]

In Formula 5, R ₇ to R ₁₀ are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and L ¹ is a substituted or unsubstituted carbon atom 1 to 20 alkylene groups or substituted or unsubstituted arylene groups having 6 to 20 carbon atoms, and n is an integer of 0 to 3.

The R ₇ to R ₁₀ may each independently be a phenyl group unsubstituted or substituted with a 'methyl group, ethyl group, isopropyl group, t-butyl group, isobutyl group, isoamyl group, or t-amyl group'.

The compound represented by Chemical Formula 5 may be, for example, tributyl phosphate, triphenyl phosphate, diphenyl octyl phosphate, tri(isopropyl phenyl) phosphate, resorcinol bridged diphosphate or bisphenol A bridged diphosphate.

The phosphorus-based flame retardant may be used alone or in a mixed form of phosphoric acid ester compounds having n values of 0, 1, 2, and 3 in Formula 5, respectively. Alternatively, phosphoric acid ester compounds having different n-values prepared separately may be mixed and used.

The content of the phosphorus-based flame retardant in the thermoplastic resin composition of the present invention may be 5 parts by weight or more, 6 parts by weight or more, 7 parts by weight or more, 8 parts by weight or more, 9 parts by weight or more, or 10 parts by weight or more based on 100 parts by weight of the total composition. and may be 20 parts by weight or less, 17 parts by weight or less, 15 parts by weight or less, 13 parts by weight or less or 11 parts by weight or less, for example 5 to 20 parts by weight, 7 to 20 parts by weight, 7 to 15 parts by weight, 7 to 13 parts by weight, or 9 to 11 parts by weight. If the phosphorus-based flame retardant is less than the above range, there may be a problem in that the flame retardant performance is lowered, and if it exceeds the above range, the content of other components is relatively reduced, and mechanical properties such as strength and appearance characteristics and extrusion processability may be deteriorated. can

(5) inorganic filler

The polyamide/polyester alloy resin composition of the present invention also includes an inorganic filler.

Conventional inorganic fillers may be used in the polyamide/polyester alloy resin composition of the present invention without particular limitation, and examples thereof include talc, whisker, glass beads, glass flakes, glass fibers, carbon fibers, clay, kaolin, and mica. , at least one selected from the group consisting of calcium carbonate and barium sulfate may be used, and preferably glass fibers may be used.

The type of glass fiber is not particularly limited, but may be E-glass, and the glass fiber has a diameter of 8 μm to 18 μm, preferably 9 μm to 11 μm, and a length of 2 mm to 7 mm, preferably may use 3 mm to 5 mm.

The content of the inorganic filler in the polyamide / polyester alloy resin composition of the present invention is 15 parts by weight or more, 18 parts by weight or more, 20 parts by weight or more, 22 parts by weight or more, 24 parts by weight or more based on 100 parts by weight of the total composition. , 26 parts by weight or more, 28 parts by weight or more, or 30 parts by weight or more, 40 parts by weight or less, 38 parts by weight or less, 36 parts by weight or less, 34 parts by weight or less, or 32 parts by weight or less, for example 15 to 40 parts by weight, 18 to 38 parts by weight or less, 20 to 34 parts by weight or less, 22 to 32 parts by weight, 24 to 32 parts by weight, 26 to 32 parts by weight, or 28 to 32 parts by weight. When the content of the inorganic filler is less than the above range, mechanical strength is deteriorated, and when the content exceeds the above range, extrusion processability is significantly deteriorated, and surface properties are significantly deteriorated because the inorganic filler protrudes to the exterior of the molded article.

(6) Other additives

The polyamide/polyester alloy resin composition of the present invention, in addition to the above-mentioned “components,” may “additionally” contain “one or more” other additives “normally” added to “thermoplastic” resins for injection molding or extrusion “molding” compositions. For example, it may additionally contain one or more other additives selected from the group consisting of antioxidants, lubricants, ultraviolet rays, absorbers, light stabilizers, impact modifiers, matting agents, flame retardants, glidants, heat stabilizers, or mixtures of two or more of these. there is.

Specifically, “antioxidants” such as “phenol-based,” “phosphite”-based, “thioester”-based, or a mixture of two or more of these “can be used” as antioxidants, and as “active agents,” “polyethylene-based,” “ethylene-ester-based,” “ethylene glycol-glycerin,” ester-based, Montane-based, ethylene glycol-glycerin-montanic acid-based, ester-based, or a mixture of two or more of these lubricants may be used. As the optical stabilizer, benzotriazole-based compounds, hydroxyphenyltriazine-based compounds, pyrimidine-based compounds, cyanoacrylate-based compounds, or mixtures of two or more of these may be used, and the impact modifier may be acrylate-based copolymers. It is possible to use “one” or more “core-shell” structured “copolymers” selected from “ethylene-acrylate-based” copolymers, “silicone”-containing “copolymers” or “polyalkyl methacrylate-based” copolymers, etc., but is not “limited” to this. The “impact modifier” can perform “stabilization” of “excellent” and “uniform” physical properties by improving “compatibility” between thermoplastics in the composition or between components in the composition as well as the function of “impact” reinforcement. In addition, as the “flame retardant,” one or more compounds selected from “phosphate-based” compounds, “phosphonate-based” compounds, “polysiloxanes”, “phosphazene” compounds, “phosphinate-based” compounds, or “melamine-based” compounds as “substances that reduce flammability” can be used, but it is limited to these. no. The matting agent may be an “inorganic compound” or an “organic” compound, and as the “inorganic” compound, “silica,” “magnesium oxide, zirconia,” “alumina, titania,” or a mixture of two or more of these may be used, and the “organic” compound may be “crosslinked” “vinyl” air. As a copolymer, the monomer of the vinyl-based copolymer may be “one” or more “monomer” selected from “styrene,” acrylonitrile, “methyl (meth)acrylate,” “ethyl (meth)acrylate,” or “butyl (meth)acrylate.” The UV absorber, glidant and heat stabilizer are not particularly limited, and commercially available products may be used.

The content of the other additives is not particularly limited, and is an amount that can be used to add additional functions within a range that does not impair desired physical properties of the polyamide/polyester alloy resin composition of the present invention.

According to one embodiment of the present invention, the content of other additives may be 0.1 to 2 parts by weight, preferably 0.5 to 1 part by weight, based on 100 parts by weight of the total polyamide/polyester alloy resin composition of the present invention. there is. When the content of the other additives is less than 0.1 parts by weight, the effect of improving various functions according to the use of the other additives may be insignificant, and when the content of the other additives exceeds 2 parts by weight, mechanical properties may be deteriorated.

According to another aspect of the present invention, a molded article comprising the polyamide/polyester alloy resin composition of the present invention is provided.

Since the polyamide/polyester alloy resin composition of the present invention realizes excellent flame retardancy at various thicknesses and at the same time exhibits excellent flowability and dimensional stability, it requires sophisticated molding and requires high flame retardant performance and stable dimensions. It can be suitably used for manufacturing molded products such as parts and connectors.

Hereinafter, the present invention will be described in more detail through Examples and Comparative Examples. However, the scope of the present invention is not limited by these examples.

[Examples and Comparative Examples]

<Preparation of resin composition and evaluation of physical properties>

The raw materials of Examples 1 to 3 and Comparative Examples 1 to 13 were well mixed and uniformly dispersed in the composition components and contents shown in Tables 1 and 2 below, and then, using a twin screw extruder, at 200 RPM and 270 ° C. It was melt-kneaded and extruded, and then cooled in a cooling bath and then pelletized to prepare pellets. Glass fiber and phosphorus-based flame retardant were side-fed through the middle of the extruder, and an 11-barrel SUPER EP extruder (STS32HS-48V) from Korea EM Co., Ltd. was used as the extruder. The prepared pellets were dried with hot air at 100 to 120 ° C. for 4 hours, and then injection molded at a temperature of 270 ° C. to prepare resin compositions of Examples 1 to 3 and Comparative Examples 1 to 13.

The components used in this Example and Comparative Example are specifically as follows.

(A) Polyamide resin: polyamide 66 having a relative viscosity of 2.7 was used. (EPR 27, Shenma)

(B) Polyester resin: using polyethylene terephthalate having intrinsic viscosity: 0.80 dl/g. (BD chip, Huvis)

(C) Polysiloxane-polycarbonate copolymer: Si-PC resin having a silicon content of 9% by weight (ST6-3022PJ, Samyang Corporation)

(D) phosphorus-based flame retardant: phosphinate-based flame retardant (Exolit®OP1400, Clariant)

(E) Inorganic filler: glass fiber (CS-311, KCC)

(E) fluidizing agent: hyperbranched structure fluidizing agent (C-100, CYD)

In addition, with respect to the resin compositions of Examples and Comparative Examples prepared as described above, the following physical property items were measured and evaluated, and the results are summarized in Tables 1 and 2 below.

(1) Flame retardancy: measured according to the UL94 test method prescribed by Underwriter's Laboratory Inc. of the United States. This is a method of evaluating flame retardancy from the after-flame time or drip properties after contacting a burner flame for 10 seconds on a specimen of a certain size held vertically. The after-flame time is the length of time for which the specimen continues flame combustion after the ignition source is moved away, and the ignition of the surface by drip is the dripping (drip) ) It is determined through ignition by water, and the flame retardancy grade is divided as follows.

(2) Tensile strength: evaluated according to ISO 527.

(3) Flexural strength: evaluated according to ISO 178.

(4) Impact strength: evaluated based on ISO 180 (notch).

(5) Absorption rate: A disk specimen with a diameter of 80 mm and a thickness of 3 mm was prepared, and the weight was measured before immersion. At this time, the weight before immersion and the weight after immersion were compared, and the absorption rate (%) = [weight after immersion - weight before immersion) / weight before immersion] was determined that the higher the absorption rate, the higher the degree of sensitivity to moisture.

(6) Dimensional stability (thickness change): After making a disk specimen with a diameter of 80 mm and a thickness of 3 mm and measuring the thickness, the thickness was measured after storage for 24 hours in a thermo-hygrostat at a temperature of 80 ° C and a humidity of 90%. At this time, the thickness of the specimen before and after storage in the thermo-hygrostat was compared, and the thickness change (%) = [(thickness after storage in the thermo-hygrostat - thickness before storage in the thermo-hygrostat) / thickness before storage in the thermo-hygrostat] * 100 It was judged that the smaller the thickness deformation of the original plate specimen, the better the dimensional stability of the composition, and thus stable molding process was possible.

(7) Appearance surface characteristics: 3mm-thick specimens were injection-molded, and the ends of thin-film molded products lacking flow were observed to visually determine whether glass fibers protruded on the surface (relative to the condition of the surface observed with the naked eye). The grade was determined as [○ good, X-poor]).

(8) Fluidity: Spiral specimens were produced to understand the fluidity characteristics generated during molding. The same cylinder temperature (270℃ and the same mold temperature (80℃) were continuously maintained regardless of the shot number so that there was no change in flow characteristics due to temperature. For this purpose, a contact thermometer was used, and the mold temperature according to each shot number In addition, molding was performed only under the same injection pressure so as not to be affected by packing pressure, and the process time was kept the same, and in this way, the length of the spiral specimen continuously injection molded under the same conditions was measured. It was determined that the longer the spiral length, the better the flowability of the composition, and thus stable molding process is possible.

(9) Extrusion processability: The ease and difficulty of continuous extrusion due to the swell generated in the extruder die and the decrease in strength of the strand during extrusion of the composition under the same conditions were evaluated through the number of times the strand was broken. (Relatively [◎ continuous extrusion possible, ○ relatively continuous process possible, △-continuous processability weak, X-continuous processability impossible]).

[Table 1]

[Table 2]

As can be seen from Tables 1 and 2, the non-halogen flame retardant polyamide/polyethylene terephthalate alloy resin compositions of Examples 1 to 3 including the polysiloxane-polycarbonate copolymer resin, Comparative Examples 1 to 13 Compared to the resin composition, it has excellent flame retardant performance even at various thicknesses, and it was confirmed that the appearance surface characteristics, dimensional stability and flowability are also good.

As in Comparative Examples 8 and 12, when an excessive amount of polysiloxane-polycarbonate or/and inorganic filler was included, the extrusion processability was remarkably deteriorated and physical properties could not be measured.

Claims (8)

Based on 100 parts by weight of the total composition,
(1) 35 to 44 parts by weight of a polyamide resin;
(2) 5 to 32 parts by weight of a polyester resin;
(3) 2 to 13 parts by weight of a polysiloxane-polycarbonate copolymer resin;
(4) 5 to 20 parts by weight of a phosphorus-based flame retardant;
(5) 15 to 40 parts by weight of an inorganic filler;
, Polyamide / polyester alloy resin composition comprising a. The polyamide/polyester alloy resin composition according to claim 1, wherein the polyamide resin has a relative viscosity of 2.3 to 3.0. The polyamide/polyester alloy resin composition according to claim 1, wherein the polyester resin has an intrinsic viscosity of 0.6 to 1.5 dl/g. The method of claim 1, wherein the polyester resin is polyethylene terephthalate resin, polytrimethylene terephthalate resin, polybutylene terephthalate resin, polyhexamethylene terephthalate resin, polycyclohexane dimethylene terephthalate resin, any of these resins. A polyamide / polyester alloy resin composition selected from the group consisting of a polyester resin modified to be amorphous by mixing some other monomers with one or a mixture thereof. The polyamide/polyester alloy resin composition according to claim 1, wherein the polysiloxane-polycarbonate copolymer comprises a hydroxy-terminated siloxane of Formula 1 or Formula 1a and a polycarbonate block of Formula 4 below as repeating units. :
[Formula 1]

In Formula 1,
R ₁ independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 13 carbon atoms, or an aryl group having 6 to 10 carbon atoms;
R ₂ is independently an alkyl group or alkoxy group having 1 to 13 carbon atoms, an alkenyl group or alkenyloxy group having 2 to 13 carbon atoms, a cycloalkyl group or cycloalkoxy group having 3 to 6 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or an alkenyloxy group having 2 to 13 carbon atoms. Representing an aralkyl group or aralkoxy group of 7 to 13, or an alkaryl group or alkaryloxy group of 7 to 13 carbon atoms,
R ₃ independently represents an alkylene group having 2 to 8 carbon atoms;
m is independently an integer from 0 to 4;
n is an integer from 30 to 200;
[Formula 1a]

In Formula 1a, R ₁ , R ₂ , R ₃ and m are as defined in Formula 1 above, n is an integer from 15 to 100, and A represents a structure of Formula 2 or 3 below.
[Formula 2]

In Formula 2, X is Y or NH-Y-NH, where Y is a linear or branched aliphatic group having 1 to 20 carbon atoms, a cycloalkylene group, or a halogen atom, an alkyl group, an alkoxy group, an aryl group, or a carboxyl group. Representing a substituted or unsubstituted mononuclear or polynuclear arylene group having 6 to 30 carbon atoms,
[Formula 3]

In Formula 3, R ₄ represents an aromatic hydrocarbon group having 6 to 30 carbon atoms or a mixed aromatic/aliphatic hydrocarbon group, or an aliphatic hydrocarbon group having 1 to 20 carbon atoms;
[Formula 4]

In Formula 4, R ₅ is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an alkenyl group having 2 to 13 carbon atoms, an alkoxy group having 1 to 13 carbon atoms, a halogen atom, or a nitro substituted or unsubstituted group. represents an aromatic hydrocarbon group having 6 to 30 carbon atoms. The polyamide/polyester alloy resin composition according to claim 1, wherein the phosphorus-based flame retardant is represented by Formula 5 below:
[Formula 5]

In Formula 5, R ₇ to R ₁₀ are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and L ¹ is a substituted or unsubstituted carbon atom 1 to 20 alkylene groups or substituted or unsubstituted arylene groups having 6 to 20 carbon atoms, and n is an integer of 0 to 3. The polyamide/polyester alloy resin composition according to claim 1, wherein the inorganic filler is a glass fiber. A molded article comprising the polyamide/polyester alloy resin composition according to any one of claims 1 to 7.